The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a transoid fashion (n-BuAu ) have been prepared by azide−alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.
A set of alkynyl-tris(2-pyridyl)phosphine Au(I) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely ‘scorpionate’ PPy3 and C≡C bond, allowed these ditopic metalloligands to be...
A series of compounds P1–P4 bearing
terminal alkynyl sites connected with a phosphonium group via different
π-conjugated linkers have been synthesized. The compounds themselves
are efficient push–pull emitters and exhibit bright fluorescence
in blue and near-UV regions. P1–P4 were used as alkynyl ligands to obtain a series of homoleptic bis-alkynyl
Au(I) complexes 1–4. The complexes
demonstrate bright phosphorescence and dual emission with dominating
phosphorescence (2–4). Terphenyl derivative complex 3 exhibits warm white emission in DMSO solution and pure white
emission in PMMA films. Time-dependent density functional theory calculations
have shown that the T1 excited state has a hybrid MLCT/ILCT
nature with a dominant contribution of charge transfer across a ligand-centered
“D-π-A” system. The variation of linker allows
tuning the effect of intermolecular charge transfer and thus changing
the electronic and photophysical properties of the organogold “D-π-A”
system. The results presented unambiguously display the advances of
the conception of organometallic “D-π-A” construction.
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